Composites: Part A 70 (2015) 35–44

Contents lists available at ScienceDirect

Composites: Part A
journal homepage: www.elsevier.com/locate/compositesa

Effect of ZnO nanoparticles doped graphene on static and dynamic

mechanical properties of natural rubber composites
Yong Lin, Yizhong Chen, Zhikai Zeng, Jiarong Zhu, Yong Wei, Fucheng Li, Lan Liu ⇑
College of Materials Science and Engineering, Key Lab of Guangdong Province for High Property and Functional Macromolecular Materials, South China University of
Technology, Guangzhou 510640, PR China

a r t i c l e i n f o a b s t r a c t

Article history: In this work, effect of ZnO nanoparticles doped graphene (Nano-ZnO–GE) on static and dynamic mechan-
Received 22 August 2014 ical properties of natural rubber composites were studied. Nano-ZnO–GE was synthesized by sol–gel
Received in revised form 22 October 2014 method and thermal treatment. With the incorporation of nano-ZnO–GE into the matrix, the mechanical
Accepted 11 December 2014
properties of NR nanocomposite significantly improved over that of NR composite containing with 5 phr
Available online 18 December 2014
of conventional-ZnO. The results demonstrated that the presence of nano-ZnO on the surface of graphene
sheets not only conduces to suppressing aggregation of graphene sheets but also acts as a more efficient
Keywords:
cure-activator in vulcanization process, with the formation of excellent crosslinked network at low
A. Polymer-matrix composites (PMCs)
A. Nano-structures
nano-ZnO–GE content. This work also showed that NR/Nano-ZnO–GE nanocomposites exhibited higher
B. Mechanical properties wet grip property and lower rolling resistance compared with NR/Conventional-ZnO composite, which
E. Cure makes nano-ZnO–GE very competitive for the green tire application as a substitute of conventional-
ZnO, enlarging versatile practical application to prepare high-performance rubber nanocomposites.
Ó 2014 Elsevier Ltd. All rights reserved.

1. Introduction
Polymer nanocomposites, generally acknowledged as indis-
pensable engineering materials, can be tailored by adding nano-
scale fillers to meet the demands in the specific properties and
versatile practical applications. Very recently, graphene (GE) as a
promising nanoscale filler has been drawn considerable interest
for preparing high performance of polymer/GE nanocomposites
owing to its unique structural, physical and chemical properties.
To date, several existing routes have been proposed to produce
GE, such as chemical vapor deposition (CVD) [1], solvothermal syn-
thesis [2], liquid-phase exfoliation of graphite [3], and chemical
reduction of exfoliated graphite oxide (GO) [4,5]. However, chem-
ical reduction of exfoliated GO has been found to be the best and
most economic for the large-scale production generally adopted
by most researchers. The large amount of oxygen-containing
groups bonding to the exfoliated GO sheets can be removed effi-
ciently upon the reduction by reducing agents. Nevertheless, GE
accomplished by the chemical reduction is inclined to agglomerate
owing to their hydrophobic nature, high specific surface area and
⇑ Corresponding author. Tel.: +86 20 87114857.
E-mail address: psliulan@scut.edu.cn (L. Liu).
van der Waals interaction [6,7], which greatly degrades the unique
properties of GE. To efficiently prevent aggregation of GE sheets, it
is desirable, therefore, to develop a method for solving this issue. In
recent years, GE/inorganic nanocomposites, derived from the dec-
oration of GE sheets with inorganic nanoparticles, such as metal
[8], metal oxide [9] and sulfide [10], has attracted a great deal of
attention. It is noted that the dispersion of inorganic nanoparticles
on reduced GE sheets can weaken the van der Waals interactions
among these sheets, suppressing aggregation of exfoliated GE
sheets.
Zinc oxide nanoparticle (nano-ZnO) is a kind of inorganic mul-
tifunctional filler, which has extensive uses in rubber additives
[11], etc. Notably, most of relevant researches about nano-ZnO
focused on using them as a substitute of conventional-ZnO and
an essential cure-activator for rubber crosslinking by sulfur or sul-
fur donors in rubber composites [11]. Conventionally, about 5 parts
per 100 parts of rubber (phr) of conventional ZnO are used in the
vulcanization of rubber. However, ZnO was classified as a hazard-
ous chemical and the European Union has stated that its applica-
tion in rubber technology should be effectively reduced and
controlled. Therefore, it is extremely anxious to reduce the ZnO
content as low as possible in making the rubber products. Due to
the larger surface area of nano-ZnO in comparison with conven-
tional-ZnO, the efficiency of nano-ZnO during vulcanization can

http://dx.doi.org/10.1016/j.compositesa.2014.12.008
1359-835X/Ó 2014 Elsevier Ltd. All rights reserved.
36 Y. Lin et al. / Composites: Part A 70 (2015) 35–44
be greatly enhanced by the maximization of the contact between
the nano-ZnO and the accelerators in the compound. In consider-
ation of this fact, nano-ZnO can be served as a more high-efficiency
activator for rubber crosslinking,
To prevent the aggregation of GE and reduce the ZnO content
with enhancing the performance of rubber nanocomposites,
nano-ZnO doped graphene (nano-ZnO–GE) is going to be an effi-
cient approach to develop multifunctional GE-based composites.
Currently, few interesting studies have already been reported to
explore the potential of nano-ZnO–GE based on supercapacitors
[12] and conductors [13]. It is surprisingly noted that no related
researches have involved the preparation, characterization and
application of Polymer/nano-ZnO–GE nanocomposites. Thus,
nano-ZnO–GE is a promising reinforcement for application in rub-
ber composites. In this work, we focused on the synthesis of nano-
ZnO–GE and the effect of nano-ZnO–GE on the static and dynamic
mechanical properties of NR nanocomposites. Nano-ZnO–GE was
obtained through sol–gel method and thermal treatment. The
resulting nano-ZnO–GE was then incorporated into rubber matrix
to prepare NR nanocomposites. These comprehensive researches
not only study the structural characteristics of nano-ZnO–GE, but
also analyze the static and dynamic mechanical properties of NR
nanocomposites. The dispersion state of GE sheets was investi-
gated using field emission scanning electron microscopy (FESEM)
and high resolution transmission electron microscopy (HRTEM).
2. Experimental
2.1. Materials
Natural graphite powder was purchased from Qingdao Xinghua
Graphite Product Co., Ltd. Hydrazine hydrate (80%), zinc vitriol
(ZnSO47H2O) and diethanolamine (DEA, 99.9%) were provided by
Guangzhou Chemical Reagent Factory. All the reagents were of
analytical grade and were used as received without further
purification.
Natural rubber (NR) was supplied by Guangzhou Rubber Insti-
tute. Zinc oxide (Conventional-ZnO), stearic acid, N-cyclo-
hexylbenzothiazole-2-sulphenamide (CZ), 2,20 -dibenzothiazole
disulfide (DM), 2-Mercaptobenzimidazole (MB) and sulfur were
purchased from Guangzhou Longsun technology Co., Ltd. Carbon
black (CB) was obtained from Sinopharm Chemical Reagent Co.,
Ltd. All the rubber ingredients were industrial grade and used as
received.
2.2. Synthesis of nano-ZnO–GE nanocomposites
GO was synthesized from natural graphite powder by a modi-
fied Hummers method [14]. Then, 60 mg of GO was dispersed in
200 mL of deionized water with sonication for 1 h, followed by
adding 600 mg of ZnSO47H2O. DEA aqueous solution was slowly
added into the mixture with continuously stirring and then the
dark yellow colloidal sol was presented. After that, the dark yellow
colloidal gel was firstly obtained by aging for 12 h at room
temperature. In this procedure, the formed colloidal gel, as a
three-dimensional barrier, prevents the aggregation of GE sheets
upon the reduction. Subsequently, 30 lL of hydrazine hydrate
was slowly put into the colloidal gel and kept at 80 °C for 6 h.
The obtained product was isolated by filtration, washed with
deionized water. Finally, nano-ZnO–GE was obtained by dehydrat-
ing at 600 °C for 2 h. Furthermore, pure nano-ZnO and GE were also
prepared by the identical procedure for the further characteriza-
tion. Hereon, it is to be remarked that 1 g of nano-ZnO–GE
nanocomposites contains GE content of 15.5 wt%.
2.3. Preparation of NR/Nano-ZnO–GE nanocomposites
The NR/Nano-ZnO–GE nanocomposites were prepared in an
open two-roll mill following the recipe given as follows: NR,
100 phr; nano-ZnO–GE, variable; stearic acid, 2 phr; MB, 1 phr;
CZ, 1.5 phr; DM, 0.5 phr; CB, 40 phr; sulfur, 1.5 phr. First, the mas-
tication of NR took place. Afterwards, all the vulcanizing additives
except sulfur were added to NR prior to the incorporation of CB
and, finally, sulfur was added. After placing at room temperature
for 12 h, NR compounds were vulcanized in 143 °C for the opti-
mum curing time (T90). T90 was derived from the curing curves pre-
viously determined by means of a Rubber Process Analyzer (Alpha
Technologies). To investigate the influence of nano-ZnO–GE on the
performance of NR nanocomposites, a series of NR composites
were prepared containing up to 0.5, 1.0, 1.5, and 2.0 phr of nano-
ZnO–GE, corresponding to GE contents of 0.0775, 0.1550, 0.2325,
and 0.3100 phr, respectively. For comparison, NR composites with
5 phr of conventional-ZnO, NR nanocomposites containing 0.0775,
0.1550, 0.2325, and 0.3100 phr of GE, and NR nanocomposites with
the incorporation of 0.4225, 0.8450, 1.2675 and 1.6900 phr of pure
nano-ZnO were also prepared by the identical procedure, respec-
tively. Hereon, these vulcanizates are abbreviated as ‘‘Nano-ZnO–
GE-x’’, ‘‘Conventional-ZnO-x’’, ‘‘GE-x’’ or ‘‘Nano-ZnO-x’’ below. The
unknown number x denotes nano-ZnO–GE, conventional-ZnO, GE
or nano-ZnO content (phr) in the composites.
2.4. Characterization
Fourier transform infrared spectroscopy (FT-IR) spectra were
collected on the Bruker VERTEX70 FTIR spectrometer. X-ray dif-
fraction (XRD) analysis were carried out using a Bruker D8 Advance
X-ray diffractometer with Cu Ka radiation (k = 0.1542 nm), and the
goniometer scanned diffracted X-rays at a scan speed of 0.15°s1.
Raman spectroscopy (LabRAM Aramis, France) with a 532.8 nm
laser excitation was used to confirm the synthesized samples.
The morphology and composition of the synthetic materials were
examined by field emission scanning electron microscopy (FESEM,
NOVA NANOSEM 430) and high resolution transmission electron
microscopy (HRTEM, JEOL2100). Mechanical properties were eval-
uated using a universal testing machine (U-CAN UT-2060, Taiwan)
at room temperature with relative humidity about 65%. For tensile
tests, the dumbbell-shaped specimens were tested at a cross-head
rate of 500 mm/min according to a China Standard GB/T 528–1998.
The samples were mechanically cut into the approximate test sec-
tion dimensions of 25  4  1.0 mm. For tear tests, the un-nicked
90° angle test pieces with 1 mm thickness were stretched at a
cross-head rate of 500 mm/min according to a China standard
GB/T 529-1999. The modulus, tensile strength, elongation at break,
and tear strength were obtained by taking an average for five spec-
imens. The measurement of crosslink density was determined by
Magnetic Resonance Crosslink Density Analyzer (IIC XLDS-15 HT,
Germany). Dynamic mechanical analysis (DMA) was performed
using a DMA242C instruments. All tests were conducted at 1 Hz
from 120 to 80 °C by using a tensile mode at the amplitude of
10 lm, and the heating rate was set at 3 °C/min. The dimension
(length, width, thickness) of the rectangle sample strips was
8  6  1 mm.
3. Results and discussion
3.1. Structural characterization of nano-ZnO–GE
To investigate the chemical change of nano-ZnO–GE during its
chemical reduction and thermal treatment, the FTIR spectrum of
samples were recorded. As shown in Fig. 1a, the broad band around
 Y. Lin et al. / Composites: Part A 70 (2015) 35–44 37

001
GO
GO

1727
Transmittance (%)

1398
1620

1226
1043
Nano-ZnO

Intensity (a.u.)

101
Nano-ZnO

100
002
Nano-ZnO-GE

110
102

103
112
1620

1120
420 Nano-ZnO-GE
(a) (b)
430

4000 3500 3000 2500 2000 1500 1000 500 10 20 30 40 50 60 70 80

Wavenumber (cm-1) 2 Theta (degree)

(c) 441

Intensity (a.u.)
437
Nano-ZnO-GE

Nano-ZnO
Intensity (a.u.)

GO 400 450 500 550

Raman shift (cm-1)

Nano-ZnO-GE

Nano-ZnO

400 800 1200 1600 2000 2400 2800

Raman shift (cm-1)

Fig. 1. FTIR spectra (a), XRD patterns (b) and Raman spectrum (c) of GO, Nano-ZnO and Nano-ZnO–GE nanocomposites. The inset in (c) shows the Raman spectrum of Nano-
ZnO–GE nanocomposites and Nano-ZnO in a narrow range. (For interpretation of the references to color in this figure legend, the reader is referred to the web version of this
article.)

3400 cm1 originates from the hydroxyl group (AOH) of all the
samples. The oxygen-containing functional groups of GO were
revealed by the bands at 1043, 1226, 1398 and 1727 cm1, which
are assigned to CAO stretching vibrations, CAOH stretching band,
CAOAH deformation band and C@O stretching of COOH groups,
respectively. The band at 1620 cm1 can be ascribed to the skeletal
vibrations of unoxidized graphitic domains [15]. However, regard-
ing the nano-ZnO–GE nanocomposites, these bands related with
the oxygen-containing functional groups are not observed, sug-
gesting that these oxygen-containing functional groups were
almost removed in the process of chemical reduction. The band
at 1620 cm1 can be attributed to C@C stretching vibrations of
GE sheets, and the band at 1200 cm1 shows the partial presence
of functional groups. Obviously, the spectrum of nano-ZnO–GE
shows a characteristic absorption band at 430 cm1, corresponding
to the Zn–O stretching vibration of ZnO. As for nano-ZnO, it pre-
sents the band for the Zn–O stretching vibration at 420 cm1. There
is a blue shift from 420 cm1 to 430 cm1 of the absorption band
corresponding to the Zn–O stretching vibration. Such result may
be due to the formation of H-bonding between hydroxyl groups
of nano-ZnO and the residual functional groups of the GE sheets.
XRD pattern of GO, nano-ZnO and nano-ZnO–GE are shown in
Fig. 1b. The strong [0 0 1] diffraction peak of GO appearing at
2h = 10.2° is observed with an interlayer spacing of 0.87 nm, owing
to the introduction of oxygen-containing groups onto the nano-
sheets [16]. XRD data of the nano-ZnO–GE presents no any charac-
teristic peak of GO, confirming the efficient reduction of GO and
revealing that the nano-ZnO effectively suppresses the aggregation
of GE [17]. And the peaks at 31.6°, 34.4°, 36.1°, 47.3°, 56.3°, 62.6°
and 67.6° ascribed to (1 0 0), (0 0 2), (1 0 1), (1 0 2), (1 1 0), (1 0 3)
and (1 1 2) planes of ZnO show the excellent crystal structures of
ZnO, which is consistent with the diffraction peaks assigned to
pure nano-ZnO.
Raman spectroscopy is a promising method for inspecting the
ordered/disordered crystal structures of carbon materials. Fig. 1c
illustrates the featured regions of Raman spectra for GO, nano-
ZnO–GE and nano-ZnO. The D band appearing at 1353 cm1 and
G band coated at 1597 cm1 correspond to the disordered struc-
ture in the graphite lattice and the vibration of sp2-bonded carbon
atoms, respectively. The intensity ratio of the D band and G (I(D)/
I(G)) is often used to directly reflect the defects of GE and monitor
the functionalization of GE. In comparison to GO, I(D)/I(G) of nano-
ZnO–GE is increased, suggesting the decrease in the average size of
sp2 domains during reduction [18–23]. The conjugated sp2 carbon
network is re-established after the reduction of GO. The re-estab-
lished sp2 carbon network size is usually small compared to the
original graphite layer, which leads to an increase in the I(D)/
I(G). And it is clearly observed that the peak at 437 cm1 exhibits
significantly for nano-ZnO–GE, corresponding to the E2 mode of
the ZnO nanostructure [24]. This peak shifts to lower frequency
(441 cm1) compared with pure nano-ZnO due to the interaction
of nano-ZnO and GE sheets. Besides, one can be noticed that the
D band and G band associated with structure of GE receive much
interference and present some defects, directly suggesting nano-
ZnO were loaded onto GE surface.
TEM and SEM observations were utilized to analyze the mor-
phology of GO and nano-ZnO–GE. Fig. 2a shows the FESEM images
of GO synthesized by oxidation process. It is clearly seen that GO
38 Y. Lin et al. / Composites: Part A 70 (2015) 35–44

Fig. 2. (a and b) FESEM images of GO (a) and Nano-ZnO–GE nanocomposites (b). (c and d) HRTEM images of Nano-ZnO–GE nanocomposites. Inset: (e) EDS spectra
corresponding to the circle-marked region of Nano-ZnO–GE nanocomposites in (b). (f) The electron diffraction (ED) pattern corresponding to the circle-marked region of the
GE nanosheet in (c). (For interpretation of the references to color in this figure legend, the reader is referred to the web version of this article.)

sheets with ‘‘accordion-like’’ structure loosely and disorderly are
stacked together. Such results can be attributed to the successful
exfoliation of GO by sonication. The FESEM image of nano-ZnO–
GE nanocomposite is illustrated in Fig. 2b. It is seen that the surface
of curled GE sheets is covered by densely packed and irregularly
shaped nano-ZnO, which avoids the restack of GE sheets and dis-
plays a good combination between GE sheets and nano-ZnO. Addi-
tionally, Fig. 2c and d exhibits the HRTEM images of nano-ZnO–GE
nanocomposites. The nano-ZnO coated on the curled thin veil-like
GE sheets are obviously observed, and the diameter of nano-ZnO is
estimated to be 20–50 nm. It is worth to notice that the curled thin
veil-like GE sheets are highly transparent. Hereon, the electron dif-
fraction (ED) pattern is performed to analyze the feature of the cir-
cle-marked region of the GE sheet, shown in Fig. 2f. As noted
previously, the number of GE layers can be identified from the
ED patterns by inspecting the intensity ratio of the Bragg reflec-
tions. The resulted ED pattern implies that the inner intensity is
stronger than the outer intensity, indicating the monolayer feature
of GE sheets [25]. Furthermore, the existence of Zn atom in the
nanocomposites has been proved by the peaks of Zn atom in EDS
spectra (Fig. 2e). No other impurities are introduced during the
synthesis.
3.2. Morphology of GE sheets in NR/Nano-ZnO–GE nanocomposites
The dispersion state of the GE sheets in the matrix is one of the
most critical issues in determining the performance of the compos-
ites. FESEM and HRTEM were employed to evaluate the dispersion
state of GE sheets in the NR/Nano-ZnO–GE nanocomposites. FESEM
images of the tensile fractured surfaces of NR/Conventional-ZnO-5
composite and NR/Nano-ZnO–GE-1.5 nanocomposite are shown in
Fig. 3. As shown in Fig. 3a and b, the surface of the NR/Conven-
tional-ZnO composite is plat and smooth. With the incorporation
of nano-ZnO–GE into NR, for NR/Nano-ZnO–GE-1.5 nanocompos-
ite, an increasing roughness of fractured surfaces with convex
structure are clearly observed in Fig. 3c, result of which is derived
from that the GE sheets are wrapped with rubber chains. Besides, it
can be seen in Fig. 3d that the GE sheets are embedded in the
matrix after the tensile test, and the boundary between GE and
the matrix is obscure. Importantly, no aggregates are formed for
the vulcanizates. All of these observations indicate a good disper-
sion of GE in the matrix and the strong adhesion between GE
and NR in the NR/Nano-ZnO–GE nanocomposites.
Furthermore, the dispersion of the GE sheets in the NR/Nano-
ZnO–GE-1.5 nanocomposite was detected by HRTEM micrographs,
exhibiting in Fig. 4a and b. Owing to the atomic number contrast
between GE and NR is very low, the contrast of the images is not
very high. This is also reported according to other studies
[26,27]. As can be seen from Fig. 4a, the agglomerates of GE sheets
cannot be observed in the TEM image, which may be contributed to
that the nano-ZnO loaded on the surface of GE hindered the
reunion of GE sheets during the preparation of NR nanocomposites.
For a higher magnification in Fig. 4b, it is clearly observed that the
GE sheets remain as individual layers, as highlighted by the red
arrows. Thus, we believe that the GE sheets do not generate
agglomeration and uniformly dispersed throughout the NR/Nano-
ZnO–GE matrix. For comparison, as for NR/GE-0.2325 nanocom-
posite, as shown in Fig. 4c, apparent stacking of GE sheets is
observed in the TEM image. This is attributed to the distance
between GE sheets in NR latex at high GE content greatly
decreased, and the GE sheets were inclined to agglomerate due
to the faster aggregation rate of GE sheets than NR latex particles
when flocculant is added [28,29]. Additionally, Fig. 4d presents
the HRTEM images of NR composites prepared by simply mixing
1.2675 phr nano-ZnO and 0.2325 phr GE with the matrix. It is seen
that the strong tendency of the monolayeric graphene sheets to
agglomerate into multilayeric graphite clearly exhibits. Thus, the
nano-ZnO coated on the GE sheets contributed to suppressing
the aggregation of GE sheets. Due to a good combination and inter-
action between GE sheets and nano-ZnO, verified by FTIR analysis
 Y. Lin et al. / Composites: Part A 70 (2015) 35–44 39

Fig. 3. FESEM images of the cross-section of the NR/Conventional-ZnO-5 composite (a-b) and NR/Nano-ZnO–GE-1.5 nanocomposite (c and d) after tensile test. (For
interpretation of the references to color in this figure legend, the reader is referred to the web version of this article.)

Fig. 4. HRTEM images of NR/Nano-ZnO–GE-1.5 nanocomposite (a and b), NR/GE-0.2325 nanocomposite (c), and NR composite prepared by simply mixing 1.2675 phr nano-
ZnO and 0.2325 phr GE with the matrix (d). (For interpretation of the references to color in this figure legend, the reader is referred to the web version of this article.)
40 Y. Lin et al. / Composites: Part A 70 (2015) 35–44
and Raman spectroscopy, the good dispersion of GE sheets can
greatly facilitate the dispersion of nano-ZnO into the matrix.
As clearly shown in Fig. 5a, a broad diffraction peak is observed
for NR, indicating a noncrystalline structure. And the XRD patterns
of all NR/Nano-ZnO–GE nanocomposites are similar to that of NR/
Conventional-ZnO-5 composite, all without the diffraction peak for
GE, an indication that GE sheets are well-dispersed in the matrix. It
is also worth pointing out that the diffraction peaks assigned to
ZnO clearly appear for NR/Conventional-ZnO-5 composite, but
with no corresponding peaks for NR/Nano-ZnO–GE nanocompos-
ites. This strongly reveals that the vulcanization efficiency of
nano-ZnO–GE is higher than conventional-ZnO in vulcanization
process. This is due to the larger surface area of nano-ZnO can
greatly enhance the maximization of the contact between the
nano-ZnO and the rubber additives (such as accelerators, sulfur)
during the vulcanization.
In an effort to evaluate the network evolution of NR/Nano-ZnO–
GE nanocomposites, the crosslink density was recorded and the
results are presented in Fig. 5b. As expected, with increasing
nano-ZnO–GE content, the physical crosslink density increases sig-
nificantly. As the concentration of the curing ingredients is identi-
cal in all the nanocomposites, the GE sheets in nano-ZnO–GE
composites are believed to provide the physical crosslink points,
contributing to the significant increase in physical crosslink den-
sity. With respect to the nanocomposites, at low nano-ZnO–GE
content (0.5 phr) in the composite, a reduction of the total cross-
link density and the chemical crosslink density is occurred. This
result could be due to that low nano-ZnO content cannot ade-
quately facilitate the formation of intermediate complexes [30]
and activate the vulcanization process. At higher nano-ZnO–GE
content, a significant increase in the crosslink density can be pre-
sented. Therefore, the integrated results show that the new gener-
ated single sulfur bond or multi-sulfur bond will be formed in the
presence of adequate nano-ZnO–GE, followed by developing to
constitute the crosslinking network.
3.3. Mechanical performance of NR/Nano-ZnO–GE nanocomposites
The effect of Nano-ZnO–GE content on the mechanical proper-
ties of NR nanocomposites is illustrated in Fig. 6. It is evident that
mechanical properties of NR/Nano-ZnO–GE-1 nanocomposite are
similar to that of NR/Conventional-ZnO-5 composite. And the NR/
Nano-ZnO–GE nanocomposites exhibit superior mechanical prop-
erties to that of NR/Conventional-ZnO composite at higher nano-
ZnO–GE content. By comparison with NR/Conventional-ZnO com-
posite, with increasing the nano-ZnO–GE content to 1.5 phr, tensile
strength, modulus at 300% strain and tear strength dramatically
are enhanced to 31.12 MPa, 9.96 MPa and 109.63 KN/m, increasing
by 12.7%, 3.8% and 32.3%, respectively. Apparently, the modulus at
(a) Conventional-ZnO-5
Nano-ZnO-GE-0.5
Nano-ZnO-GE-1.0
Intensity (a.u.)
Nano-ZnO-GE-1.5
Nano-ZnO-GE-2.0
20 40 60
2 Theta (degree)
Fig. 5. XRD patterns (a) and the crosslinked density analysis (b) of NR/Conventional-ZnO-5 composite and NR/Nano-ZnO–GE nanocomposites. (For interpretation of the
references to color in this figure legend, the reader is referred to the web version of this article.)
300% strain and tear strength exhibit a similar trend to that of ten-
sile strength. Nevertheless, the elongation at break of nanocompos-
ites decreases with increasing the nano-ZnO–GE content, resulting
from that high GE content produces more physical crosslink points
which limit the slippage of rubber chains, and higher nano-ZnO
content effectively activates the vulcanization process for matur-
ing the crosslinking network. Hence, it is reasonable to conclude
that low nano-ZnO–GE content provides larger reinforcing effi-
ciency in mechanical properties of NR nanocomposites than higher
conventional-ZnO content. To further verify the reinforced effi-
ciency of nano-ZnO–GE on NR composites, NR/GE nanocomposites
and NR/Nano-ZnO nanocomposites were regarded as the reference
samples for analysis. Compared with NR/GE-0.2325 nanocompos-
ite, the tensile strength, modulus at 300% strain and tear strength
of NR/Nano-ZnO–GE-1.5 composite (contents 0.2325 phr GE) are
increased by 5.2%, 1.4% and 22.4%, respectively. Moreover, it is
noticeable that the mechanical properties for NR/Nano-ZnO–GE
composites are much higher than those for NR/Nano-ZnO nano-
composites. The tensile strength, modulus at 300% strain and tear
strength of NR/Nano-ZnO–GE-1.5 nanocomposite is 6.7%, 5.1% and
20.9% higher than those for NR/Nano-ZnO-1.2675 nanocomposite.
This can be attributed to the improved dispersion of GE sheets in
the NR nanocomposites with the addition of Nano-ZnO–GE. Mean-
while, the uniform dispersed GE can act as high efficiency rein-
forcement. And the nano-ZnO with large surface area, coated on
the GE sheets, can greatly enhance the vulcanization efficiency
by maximizing the contact between the nano-ZnO and rubber
additives, which also contributes to the enhancements of the
mechanical properties. These results indicate that nano-ZnO–GE
provides larger reinforcing efficiency in mechanical properties of
NR nanocomposites than GE and pure nano-ZnO.
Surprisingly, a substantial increase in the tear strength is
observed for NR/Nano-ZnO–GE nanocomposites (expect the addi-
tion of 0.5 phr nano-ZnO–GE content) as compared with NR/Con-
ventional-ZnO-5 composites. The tear strengthes of NR/Nano-
ZnO–GE nanocomposites are increased by 25.2%, 32.3% and 37.0%
at 1.0 phr, 1.5 phr and 2 phr nano-ZnO–GE, respectively. Fig. 7 is
the digital photographs of tear behavior for NR composites before
and after fracture. As illustrated in Fig. 7b, the samples for NR/Con-
ventional-ZnO-5 composite and NR/Nano-ZnO–GE-0.5 nanocom-
posite are torn into a ‘‘fine crack’’ with ‘‘perfectly sharp’’ ends. It
is the large stress concentration at the right-angled cut or the tip
of a sharp crack that causes the stress can afford to tear a specimen.
Obviously, a significant increase in tear strength is observed with
the incorporation of higher content of nano-ZnO–GE. It is also
clearly seen that an ‘‘anomalistic crack’’ with ‘‘irregular sharp’’
ends display before and after fracture. Herein, two possible reasons
are proposed as demonstrated in Fig. 8a. Firstly, the GE sheets are
uniformly dispersed in the matrix, as observed from the TEM
Total crosslinked density
14 (b)
Physical crosslinked density
Crosslinked density
Chemical crosslinked density
(×10-5 mol/cm3)
12
10
4
80 0.0 0.5 1.0 1.5 2.0
Nano-ZnO-GE content (phr)
 Y. Lin et al. / Composites: Part A 70 (2015) 35–44 41

Fig. 6. Comparison of mechanical properties of NR/Nano-ZnO–GE, NR/Nano-ZnO and NR/GE nanocomposites. (a) Tensile strength; (b) Elongation at break; (c) Modulus at
300% strain; (d) Tear strength. The symbol a represents 5 phr for conventional-ZnO, and b, v, d, e represent 0.5, 1.0, 1.5, 2.0 phr for nano-ZnO–GE, or 0.4225, 0.8450, 1.2675,
1.6900 phr for nano-ZnO, or 0.0775, 0.1550, 0.2325, 0.3100 phr for GE, respecitvely. (For interpretation of the references to color in this figure legend, the reader is referred to
the web version of this article.)

Fig. 7. Comparison of tear behavior for NR/Conventional-ZnO-5 composite and NR/Nano-ZnO–GE nanocomposites before (a) and after (b) fracture.

observations. The homo-dispersion of GE sheets can be in favor of
avoiding the stress concentration of the cracks and dissipating
energy during the tearing process. Simultaneously, the GE sheets
with high specific surface area can also prevent the expansion of
the crack, leading to a very efficient load transfer from the matrix
to GE sheets. Secondly, NR nanocomposites tend to adjust to those
large stress gradients under uniaxial stretch, by the formation of
strain-induced crystallization (SIC) at the tip of the cut. The SIC
plays an important role in preventing crack growth of the compos-
ite under large deformation, and determining its tear strength
42
(a)
(b)
(200)
Nano-ZnO-GE-2.0
Intensity (a.u.)
Nano-ZnO-GE-1.5
Nano-ZnO-GE-1.0
Nano-ZnO-GE-0.5
Conventional-ZnO
Blank sample
5 10 15
2 Theta (degree)
Fig. 8. (a) Schematic of SIC behavior of NR/Nano-ZnO–GE nanocomposites under uniaxial stretch. (b) XRD patterns of NR nanocomposites as a function of 300% strain under
stretching at the 2h angle range of 5–30°. (c) The shift of the CAH out-of-plane absorption band upon crystallization of stretching NR composites. Blank sample refers to the
NR/Conventional-ZnO-5 composite untreated by uniaxial stretch. (For interpretation of the references to color in this figure legend, the reader is referred to the web version of
this article.)
[31,32]. Hence, XRD was conducted to investigate the SIC behavior
of NR composites under uniaxial stretch, as shown in Fig. 8b. Under
uniaxial stretch at 300% strain, two peaks are appearing at
2h = 15.1° and 2h = 22.0°, which are ascribed to the [2 0 0] crystalli-
zation peak and [1 2 0] crystallization peak, respectively. Compared
with NR/Conventional-ZnO composite, low nano-ZnO–GE content
leads to an increase in the strength of the crystallization peaks
for NR/Nano-ZnO–GE composites, then the strength of the crystal-
lization peaks present an enhancing trend as the increase of nano-
ZnO–GE content. It is concluded that nano-ZnO–GE is more effi-
cient in the formation of SIC than conventional-ZnO. Furthermore,
the FTIR spectra of NR composites were recorded to investigate the
effect of SIC behavior on the network rearrangement. As demon-
strated in Fig. 8c, all the spectra of composites have similar profiles.
For NR/Conventional-ZnO-5 composite, it is interesting that the
band located at 820 cm1 associated with the CAH out-of-plane
bending mode of the cis-unit of the natural rubber macromolecular
chains is shifted to higher wavenumber (833 cm1) on stretching.
This shift is attributed to the SIC of NR composites [33]. It is note-
worthy that, the band corresponding to the CAH out-of-plane
bending mode for NR/Nano-ZnO–GE nanocomposites is signifi-
cantly shifted to the higher wavenumber compared with that of
NR/Conventional-ZnO-5 composite. This phenomenon is due to
that the newly formed SIC behavior has a great effect on the con-
figuration deformation of CAH out-of-plane bending mode of
AC(CH3)@CAH in NR/Nano-ZnO–GE nanocomposites. Thus, using
nano-ZnO–GE as a cure activator during the vulcanization process,
it greatly promotes the formation of much SIC, and the load can be
transferred onto the crystallization points, effectively facilitating
the energy dissipation. Such results cause that the samples present
the ‘‘imperfect shape’’ ends for NR/Nano-ZnO–GE-1.5 and NR/
Nano-ZnO–GE-2.0 nanocomposites. Therefore, the more striking
reinforcing efficiency of nano-ZnO–GE on tear strength of NR com-
posites is originated from the homo-dispersion of GE sheets and
the formation of much strain-induced crystallization, which ensure
efficient energy dissipation.
Y. Lin et al. / Composites: Part A 70 (2015) 35–44
(c) Nano-ZnO-GE-2.0
(120)
841
Nano-ZnO-GE-1.5
838
Transmittance (%)
Nano-ZnO-GE-1.0
835
Nano-ZnO-GE-0.5
825
Conventional-ZnO-5
833
Blank sample
820
C-H bend in -C(CH3)=CH-
20 25 30 1600 1400 1200 1000 800
Wavenumber (cm-1)
3.4. Dynamic mechanical properties of NR/Nano-ZnO–GE
nanocomposites
To examine the reinforcing efficiency of nano-ZnO–GE on the
performance of NR nanocomposites, DMA measurements were
performed to investigate dynamic mechanical properties. The log-
arithms of the storage modulus (E0 ) and the loss factor (tan d) of NR
composites versus temperature are depicted in Fig. 9a and b,
respectively. The E0 values of the NR/Nano-ZnO–GE nanocompos-
ites with nano-ZnO–GE content (high than 1.0 phr) show a signif-
icant improvement compared to that of NR/Conventional-ZnO-5
composite, indicating that the elastic response of NR nanocompos-
ites with the lower content of nano-ZnO–GE towards deformation
is superior to that of NR/Conventional-ZnO-5 composite. Also, tan d
of rubber composites, representing the ratio of the viscous part to
the elastic part (energy loss/energy stored), is an indicator of how
efficiently the material loses energy due to molecular rearrange-
ments and internal friction. As shown in Fig. 9b, a glass transition
region is observed in the curves of tan d versus temperature. For
that, the glass transition temperature (Tg) of the NR/Nano-ZnO–
GE nanocomposites is calculated from the peak of the curve, as
depicted in Table 1. In comparison with NR/Conventional-ZnO
composite, Tg of the NR/Nano-ZnO–GE nanocomposites is obvi-
ously shifted to a higher temperature because of the increasing
ratio of GE sheets and the increase in the crosslink density, which
restricts the motion of the rubber molecular chains [34].
Besides, it is worth mentioning that the tan d at 60 °C and 0 °C,
as two important indexes for high-performance rubber production
(such as tire), represent rolling resistance and wet grip property,
respectively. More recently, to achieve the goal with energy con-
servation, environmental protection, security and durability,
‘‘green’’ tire materials with low rolling-resistance and high wet
grip property has drawn tremendous attention in rubber industry,
especially in carbon black reinforced rubber composite which is
currently used in preparing passenger tire. But for the carbon black
reinforced rubber composite, the rolling resistance of composite
 Y. Lin et al. / Composites: Part A 70 (2015) 35–44 43

1.0
Conventional-ZnO-5 0.25
Nano-ZnO-GE-0.5 (b)
0.8
Nano-ZnO-GE-1.0 0.20

Tan δ
1000 Nano-ZnO-GE-1.5

Log E' (MPa)

Nano-ZnO-GE-2.0 0.6 0.15

Tan δ
0.10
0.4 0 20 40 60
Temperature (οC)
100
0.2
Conventional-ZnO-5
0.0 Nano-ZnO-GE-0.5 Nano-ZnO-GE-1.5
(a) Nano-ZnO-GE-2.0
10 Nano-ZnO-GE-1.0

-120 -80 -40 0 40 80 -120 -80 -40 0 40 80

Temperature (οC) Temperature (οC)

Fig. 9. Values of E0 (a) and tan d (b) of NR/Nano-ZnO–GE nanocomposites and NR/Conventional-ZnO-5 composite as a function of temperature. (For interpretation of the
references to color in this figure legend, the reader is referred to the web version of this article.)

Table 1
Summary of DMA results of NR nanocomposites with different nano-ZnO–GE
contents.
Samples Tan d (0 °C) Tan d (60 °C)
Conventional-ZnO-5 0.178 0.139
Nano-ZnO–GE-0.5 0.181 0.146
Nano-ZnO–GE-1.0 0.206 0.184
Nano-ZnO–GE-1.5 0.189 0.132
Nano-ZnO–GE-2.0 0.180 0.125
always presents an opposite trend with the wet grip property. By
preparing NR composites with nano-ZnO–GE as a substitute of
conventional-ZnO, the result demonstrates that, when the nano-
ZnO–GE content is up to 1.5 phr, wet grip property are about
5.0% higher than that of the NR/Conventional-ZnO-5 composite,
and rolling resistance is reduced by 6.2% compared to that of NR/
Conventional-ZnO-5 composite. Furthermore, as for NR/Nano-
ZnO–GE-2.0 nanocomposites, the rolling resistance of nanocom-
posite decreases by 10.1%, but with remaining almost unchanged
in the wet grip property. As a result, NR nanocomposites with
low nano-ZnO–GE content show improved static and dynamic
mechanical properties compared with these of NR/Conventional-
ZnO-5 composite. Such promising mechanical properties make
NR/Nano-ZnO–GE nanocomposites very competitive for potential
applications as the green tire materials.
4. Conclusion
The presented work demonstrated that GE was successfully
doped by nano-ZnO using a versatile and simple approach based
on sol–gel method and dehydration treatment. Subsequently, the
synthesized nano-ZnO–GE nanocomposites were further employed
as cure activator to prepare homogeneous NR/Nano-ZnO–GE nano-
composites. The densely packed and irregularly shaped nano-ZnO
not only suppresses the aggregation of GE sheets but also effec-
tively promotes constituting the crosslinking network. The results
also verified that NR nanocomposites with lower nano-ZnO–GE
content showed greatly improved static and dynamic mechanical
properties as compared with NR/Conventional-ZnO-5 composite.
And the NR/Nano-ZnO–GE nanocomposites exhibit superior
mechanical properties to these of NR/Nano-ZnO nanocomposites
and NR/GE nanocomposites. With adding 1.5 phr of nano-ZnO–
GE, tensile strength, modulus at 300% strain and tear strength dra-
matically enhances to 31.12 MPa, 9.96 MPa and 109.63 KN/m,
increasing by 12.7%, 3.8% and 32.3%, respectively. Wet grip prop-
erty of nanocomposites is enhanced by 5.0%, and rolling resistance
is reduced by 6.2%. Thus, NR/Nano-ZnO–GE nanocomposites
exhibited very competitive for the green tire application. This work
might expedite synthesis of the multi-functional GE-based materi-
als for enhancing rubber composites, and provides a new insight
Tg (°C) into the fabrication of high-performance rubber composites for
59.1 future engineering applications.
58.9 Acknowledgements
56.2
55.0
54.4 The authors gratefully acknowledge ‘‘National Natural Science
Foundation of China’’ (contract Grant number: U1134005), ‘‘the
Fundamental Research Funds for the Central Universities, South
China University of Technology’’ (2012ZZ0006), ’’Strategic New
Industry Core Technology Research Project of Guangdong Province
(2012A090100017), and ‘‘National Undergraduate Training Pro-
grams for Innovation’’ (201410561037) for the financial support.
References
[1] Reina A, Jia X, Ho J, Nezich D, Son H, Bulovic V, et al. Large area, few-layer
graphene films on arbitrary substrates by chemical vapor deposition. Nano Lett
2008;9:30–5.
[2] Schniepp HC, Li JL, McAllister MJ, Sai H, Herrera-Alonso M, Adamson DH, et al.
Functionalized single graphene sheets derived from splitting graphite oxide. J
Phys Chem B 2006;110(17):8535–9.
[3] Bourlinos AB, Georgakilas V, Zboril R, Steriotis TA, Stubos AK. Liquid-phase
exfoliation of graphite towards solubilized graphenes. Small 2009;5:1841–5.
[4] Li D, Muller MB, Gijle S, Kaner RB, Wallace GG. Processable aqueous
dispersions of graphene nanosheets. Nat Nanotechnol 2008;3:101–5.
[5] Park S, Ruoff RS. Chemical methods for the production of graphenes. Nat
Nanotechnol 2009;4:217–24.
[6] Si Y, Samulski ET. Synthesis of water soluble graphene. Nano Lett
2008;8(6):1679–82.
[7] Lomeda JR, Doyle CD, Kosynkin DV, Hwang WF, Tour JM. Diazonium
functionalization of surfactant-wrapped chemically converted graphene
sheets. J Am Chem Soc 2008;130:16201–6.
[8] Subrahmanyam KS, Manna AK, Pati SK, Rao CNR. A study of graphene
decorated with metal nanoparticles. Chem Phys Lett 2010;497(1–3):70–5.
[9] Yin HJ, Zhao SL, Wan JW, Tang HJ, Chang L, He LC, et al. Three-dimensional
graphene/metal oxide nanoparticle hybrids for high-performance capacitive
deionization of saline water. Adv Mater 2013;25(43):6270–6.
[10] Mahmood N, Zhang CZ, Hou YL. Nickel sulfide/nitrogen-doped graphene
composites: phase-controlled synthesis and high performance anode
materials for lithium ion batteries. Small 2013;9(8):1321–8.
[11] Panampilly B, Thomas S. Nano ZnO as cure activator and reinforcing filler in
natural rubber. Polym Eng Sci 2013;53(6):1337–46.
[12] Lu T, Pan LK, Li HB, Zhu G, Lv T, Liu XJ, et al. Microwave-assisted synthesis of
graphene-ZnO nanocomposite for electrochemical supercapacitors. J Alloys
Compd 2011;509:5488–92.
[13] Lee JM, Pyun YB, Yi J, Choung JW, Park WI. ZnO nanorod-graphene hybrid
architectures for multifunctional conductors. J Phys Chem C 2009;113:
19134–8.
[14] Li HB, Lu T, Pan LK, Zhang YP, Sun Z. Electrosorption behavior of graphene in
NaCl solutions. J Mater Chem 2009;19:6773–9.
[15] Xu YX, Bai H, Lu GW, Li C, Shi GQ. Flexible graphene films via the filtration of
water-soluble noncovalent functionalized graphene sheets. J Am Chem Soc
2008;130(18):5856–7.
[16] Zhu CZ, Guo SJ, Fang YX, Dong SJ. Reducing sugar: new functional molecules
for the green synthesis of graphene nanosheets. ACS Nano 2010;4:2429–37.
44 Y. Lin et al. / Composites: Part A 70 (2015) 35–44
[17] Cai DY, Song M. Preparation of fully exfoliated graphite oxide nanoplatelets in
organic solvents. J Mater Chem 2007;17:3678–80.
[18] Yang D, Velamakanni A, Bozoklu G, Park S, Stoller M, Piner RD, et al. Chemical
analysis of graphene oxide films after heat and chemical treatments by X-ray
photoelectron and micro-Raman spectroscopy. Carbon 2009;47:145–52.
[19] Xu Y, Bai H, Lu G, Li C, Shi G. Flexible graphene films via the filtration of water-
soluble noncovalent functionalized graphene sheets. J Am Chem Soc
2008;130:5856–7.
[20] Stankovich S, Dikin DA, Piner RD, Kohlhaas KA, Kleinhammes A, Jia Y, et al.
Synthesis of graphene-based nanosheets via chemical reduction of exfoliated
graphite oxide. Carbon 2007;45:1558–65.
[21] Tang ZH, Zeng CF, Lei YD, Guo BC, Zhang LQ, Jia DM. Fluorescent whitening
agent stabilized graphene and its composites with chitosan. J Mater Chem
2011;21:17111–8.
[22] Satheesh K, Jayavel R. Synthesis and electrochemical properties of reduced
graphene oxide via chemical reduction using thiourea as a reducing agent.
Mater Lett 2013;113:5–8.
[23] Schniepp HC, Li J, Mcallister MJ, Sai H, Herrera-Alonso M, Adamson DH, et al.
Functionalized single graphene sheets derived from splitting graphite oxide. J
Phys Chem B 2006;110(17):8535–9.
[24] Calleja M, Cardona M. Resonant Raman scattering in ZnO. Phys Rev B
1977;16:3753.
[25] Wang XQ, Fulvio PF, Baker GA, Veith GM, Unocic RR, Mahurin SM, et al. Direct
exfoliation of natural graphite into micrometre size few layers graphene
sheets using ionic liquids. Chem Commun 2010;46:4487–9.
[26] Wang X, Hu YA, Song L, Yang HY, Xing WY, Lu HD. In situ polymerization of
graphene nanosheets and polyurethane with enhanced mechanical and
thermal properties. J Mater Chem 2011;21:4222–7.
[27] Kim H, Abdala AA, Macosko CW. Graphene/polymer nanocomposites.
Macromolecules 2010;43:6515–30.
[28] Potts JR, Shankar O, Du L, Ruoff RS. Processing-morphology-property
relationships and composite theory analysis of reduced graphene oxide/
natural rubber nanocomposites. Macromolecules 2012;45:6045–55.
[29] Liu X, Sun DQ, Wang LW, Guo BC. Sodium humate functionalized graphene and
its unique reinforcement effects for rubber. Ind Eng Chem Res
2013;52:14592–600.
[30] Aprem AS, Joseph K, Thomas S. Recent developments in crosslinking of
elastomers. Rubber Chem Technol 2005;78:458–88.
[31] Stewart CW. A new mechanism for increasing tear strength and cut-growth
resistance of elastomers. J Appl Polym Sci 1993;48:809–18.
[32] Hamed GR. Tear strength of black-filled natural rubber crosslinked via
conventional and efficient sulfur cures. Rubber Chem Technol 2003;77:227–9.
[33] Amram B, Bokobza LJP, Queslel JP, Monnerie L. Fourier-transform infra-red
dichroism study of molecular orientation in synthetic high cis-1,4-
polyisoprene and in natural rubber. Polymer 1986;27(6):877–82.
[34] Etmimi HM, Sanderson RD. New approach to the synthesis of exfoliated
polymer/graphite nanocomposites by miniemulsion polymerization using
functionalized graphene. Macromolecules 2011;44(21):8504–15.